CN1651479A - Manufacturing method of biodegradable high polymer material-polylactic acid - Google Patents

Manufacturing method of biodegradable high polymer material-polylactic acid Download PDF

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CN1651479A
CN1651479A CN 200410013681 CN200410013681A CN1651479A CN 1651479 A CN1651479 A CN 1651479A CN 200410013681 CN200410013681 CN 200410013681 CN 200410013681 A CN200410013681 A CN 200410013681A CN 1651479 A CN1651479 A CN 1651479A
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polylactic acid
microwave
polycondensation
catalyst
lactic acid
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CN1280332C (en
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顾卫平
顾峪
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顾卫平
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Abstract

A process for preparing biodegradable high-molecular polylactic acid features that the monometal or bimetal nano-catalyst or the combined two-element nano-catalyst is added by multiple steps, and such techniques as negative-pressure convection of heat medium, exhausting gas, microwave irradiating, and rotary heating are used for high efficiency and output rate.

Description

生物降解高分子材料—聚乳酸的制造方法 Biodegradable polymer materials - Method for producing polylactic acid

技术领域 FIELD

本发明涉及一种可完全生物降解的高分子材料-聚乳酸的制造方法。 The present invention relates to a fully biodegradable polymer material - Method for producing polylactic acid.

背景技术 Background technique

可完全生物降解塑料聚乳酸,是利用可再生资源为原料,经生物工程技术和化学技术等工艺技术方法合成的。 Fully biodegradable plastics, polylactic acid, using renewable resources as raw materials, synthesis of a biotechnology and chemical process technology and other technology. 它以其优异的机械性能、广泛的应用领域、显著的环境效益和社会效益,被公众所瞩目和青睐,它对环境有益,是替代不可再生资源石油基塑料的良好材料。 With its excellent mechanical properties, a wide range of applications, significant environmental and social benefits, are public attention and favor, it is environmentally beneficial, is an alternative to non-renewable resources, petroleum-based plastic material of good. 现有生产的可完全生物降解高分子材料聚乳酸,不外乎有以下几种合成工艺技术方法:一种是乳酸直接脱水缩聚合成聚乳酸的生产技术方法(也叫一步聚合法);一种是乳酸经脱水剂,脱除乳酸中的水份,然后再经惰性气体保护化学合成为聚乳酸的生产技术方法;还有一种是乳酸经脱水环化生成丙交酯,在由丙交酯开环聚合成为聚乳酸的生产技术方法(也叫两步聚合法)等等技术方法,在生产上采用上述几种聚合方法,生产的可完全生物降解高分子材料聚乳酸,其工艺技术操作比较复杂、不易实现自动化、聚乳酸产收率低、反应聚合体系所用时间长、产品品质较差、成本高、耗能大、而且对环境也有污染等缺点。 The current production of fully biodegradable polylactic polymers, have no more than several synthesis technique: one is direct dehydration polycondensation of lactic acid of the polylactic acid production technology process (also called one-step polymerization); one kind lactic acid by dehydrating agent, polylactic acid production technology for removing acid in the water, and then the protective gas is an inert chemical synthesis; there is a cyclization dehydration of lactic acid lactide, lactide in the open ring polymerized to polylactic acid production technology (also called two-step polymerization method) and the like art methods, several polymerization processes in the above production, the production of fully biodegradable polymers polylactic acid, which operation is more complicated technology and difficult to automate, low yield production of polylactic acid, the polymerization reaction system used for a long time, poor product quality, cost, energy consumption, but also has disadvantages for the environment pollution. 这些缺点已不适合当今清洁生产、保护环境、降低能源消耗和生产成本等的要求,这也无疑的是阻碍了可完全生物降解高分子材料聚乳酸,在各个应用领域中的应用。 These disadvantages are not suitable for today's clean production, protect the environment, reduce energy consumption requirements and production costs, which is also undoubtedly hindered the fully biodegradable polylactic acid polymer materials, applied in various fields of application.

发明内容 SUMMARY

本发明的目的在于提供一种清洁生产、高效合成可完全生物降解的高分子材料-聚乳酸的制造方法。 Object of the present invention is to provide a clean production, efficient synthesis of fully biodegradable polymer material - Method for producing polylactic acid.

本发明优化了以往传统乳酸合成聚乳酸的生产工艺和生产技术,并首创在乳酸或乳酸混合物开环聚合或直接缩聚合成聚乳酸反应体系中,应用了“多步添加”纳米双金属催化剂及纳米单金属催化剂或“多步添加”纳米组合二元催化剂及其它应用催化剂的工艺技术方法和使用了热传导介质负压对流排气微波辐射旋转加热技术等新工艺和新技术,使乳酸或乳酸混合物高效化学聚合成为高产率的聚乳酸。 The present invention optimizes conventional traditional acid synthesized polylactic acid production technology and production technology, and the first ring-opening polymerization or the direct polycondensation of polylactic acid in the reaction system, the application of lactic acid or lactic acid mixture "Multistep Add" nano-metal catalyst and nano metal catalyst or a single "multi-step add" nano technology binary catalyst compositions and other applications of the catalyst and the heat transfer medium using the negative pressure exhaust convection microwave heating technology, rotating new processes and new technology, lactic acid or a mixture of high chemical polymerized to polylactic acid in a high yield. 该项乳酸高效率化学合成聚乳酸的生产工艺和生产技术,具有生产工艺技术操作简单、容易实现自动化、聚乳酸产收率高、反应聚合体系所用时间短、耗能和成本大大降低、产品品质好、反应聚合体系无三废排放污染等优点。 The high efficiency of the chemical synthesis of poly lactic acid production process and production technology, production technology is simple, easy to automate, and high yield production of polylactic acid, the polymerization reaction system used short time, energy and costs are significantly reduced, the quality of the product well, the polymerization reaction system without waste pollution emissions advantages. 这些优点无疑是大大的提高了聚乳酸,在高分子降解材料市场上的竞争力,使可完全生物降解高分子材料聚乳酸,有效的在环境保护领域和各个应用领域中,发挥着更大的作用,同时也达到了聚乳酸清洁生产高效合成的目的。 These advantages are undoubtedly greatly improve the polylactic acid, polymer degradation competitive in the materials market, the fully biodegradable polylactic acid polymer materials, and effective in various applications in the field of environmental protection, play a greater action, but also achieve the purpose of production of polylactic acid cleaner and efficient synthesis.

本发明的技术方案是:本发明采用两种方案,由乳酸或乳酸混合物,经扩链剂扩链和“多步添加”纳米级催化剂和热传导介质负压对流排气微波辐射旋转加热技术直接缩聚或开环聚合合成高产率聚乳酸的最佳工艺技术路线和最佳聚合或缩聚合成反应体系技术方案,使乳酸高效率、无三废排放污染、化学聚合、高产率的聚乳酸。 Aspect of the present invention are: the present invention uses two solutions of lactic acid or a mixture, the chain extender, the chain extender and "multi-step add" nanoscopic catalyst and convection heat transfer medium vacuum exhaust rotary microwave heating technology direct polycondensation or ring-opening polymerization of polylactic acid synthesized in high yield the best technology and best route polycondensation or polymerization reaction system aspect, lactic acid efficiently without waste and pollution, chemical polymerization of polylactic acid in high yield.

方案一(属直接缩聚法)乳酸或乳酸混合物缩聚合成聚乳酸的工艺技术路线和缩聚合成技术方案:1.工艺技术路线:本“方案一”可采用两种工艺技术路线,完成乳酸缩聚合成聚乳酸。 A program (which is a direct polycondensation method) lactic acid or a mixture of polylactic acid polycondensation and polycondensation technology aspect routes: Route 1 Technology: present "Program a" route may employ two kinds of technology, to complete the synthesis of poly-lactic acid polycondensation lactic acid.

(1).乳酸中加入扩链剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热乳酸预扩链脱水处理,在脱水后乳酸中加入纳米双金属催化剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热扩链预缩聚,预缩聚产物加入纳米单金属催化剂经热传导介质负压对流排气微波辐射旋转加热缩聚或聚合得聚乳酸。 (1) Lactic acid is added to the chain extender, by conventional heating or heat transfer media of negative pressure convection exhaust microwave radiation heating rotatable acid pre chain dehydration treatment, the addition of nano-metal catalyst dehydrated lactic acid, by conventional heating or a heat transfer medium vacuum exhaust convection microwave heating rotatable chain precondensation, precondensation product is added to the metal catalyst nano single heat transfer medium through the negative pressure exhaust convection microwave heating rotatable polycondensation or polymerization to obtain polylactic acid.

(2).乳酸中加入扩链剂和纳米组合二元催化剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热乳酸连续脱水扩链缩聚,缩聚产物加入纳米组合二元催化剂经热传导介质负压对流排气微波辐射旋转加热缩聚或聚合得聚乳酸。 (2) lactic acid was added chain extenders and nano binary catalyst composition by conventional heating or convection heat transfer media vacuum exhaust continuous microwave heating rotatable acid chain dehydration condensation, polycondensation product adding nano binary catalyst composition by a heat transfer medium vacuum exhaust convection microwave heating rotatable polycondensation or polymerization to obtain polylactic acid.

2.技术工艺阐述:a.本“方案一”所涉及的乳酸原料可以是D-乳酸、L-乳酸和DL-乳酸,也可以是D、L、DL其中的一种或两种与其它单体物质的一种或两种混合原料,乳酸原料纯度为50%工业级-99.8%高纯度医用级均可。 2. art processes described:. A present "Program a" involved lactic acid feedstock can be D-, L- and DL- lactic acid, may be D, L, DL and wherein one or both of the other single one kind of substance or two of the mixed raw material, the raw material lactic acid 50% purity technical grade -99.8% high purity medical grade available.

b.本“方案一“可以选用的聚合纳米级催化剂为元素周期表中的:I族、II族、III族、IV族、V族和镧系中的金属、金属氧化物及金属盐类中的一种或两种或两种的组合作为聚合体系的纳米单金属催化剂或纳米双金属催化剂,如锌、锡、钛、镧、氧化锌、三氧化二锑、二氧化钛、三氧化二镧、氯化亚锡、辛酸亚锡、醋酸锡、辛酸锡与氧化锌的复合、氧化锌与三氧化二锑的复合、氧化锌与三氧化二镧的复合等等;还有由羧酸盐类与对甲苯基磺酸复合的纳米组合二元催化剂:辛酸亚锡与对甲苯基磺酸的复合、乳酸锌与对甲苯基磺酸的复合、SnCl2·2H2O与对甲苯基磺酸的复合等等。 . B This "one embodiment" can be selected as a polymerization catalyst nanoscale periodic table: I group, II group, III group, IV group, V and lanthanoid metal, metal oxide and metal salts of one or a combination of two or nano polymerization system as a single nano-metal catalysts or metal catalysts, such as zinc, tin, titanium, lanthanum, zinc oxide, antimony trioxide, titanium oxide, lanthanum oxide, chloride stannous, stannous octoate, tin acetate, tin octylate and zinc composite oxide, a composite oxide of zinc and antimony trioxide, zinc oxide and lanthanum oxide composite and the like; and the salts of carboxylic acid toluene sulfonic acid compound nanocomposite binary catalyst: stannous octoate and toluene sulfonic acid compound, zinc lactate and p-toluene sulfonic acid compound, SnCl2 · 2H2O composite toluene sulfonic acid and the like pairs. 可选用的扩链剂为:二异氰酸酯、季戊四醇、二酸酐、山梨醇、邻苯四甲酸、二环氧化物类、二唑啉类等等。 Optional chain extenders are: diisocyanates, pentaerythritol, anhydride, sorbitol, phthalic acid, diepoxides, oxadiazoles morpholines and the like.

“催化剂”,作为乳酸缩聚或聚合反应体系中的重要元素,它起着承上启下、加速促进反应体系的进程和反应物的生成及反应物的产率,因而在反应体系中起到重要的作用。 "Catalyst", as the polycondensation of lactic acid or the polymerization reaction system is an important element which plays the nexus, and promote the formation of the acceleration process and the yield of the reaction product of reactants the reaction system, and thus play an important role in the reaction system. 所以在本“方案一”中,所选用的催化剂均为无毒副作用、催化活性较高,并首创在乳酸或乳酸混合物缩聚或聚合聚乳酸化学反应体系中,应用了“纳米单金属催化剂”和“纳米双金属催化剂”及“纳米组合二元催化剂”等纳米级催化剂。 Therefore, "an embodiment" of the present, the choice of catalyst are toxic side effects, a high catalytic activity, and the first polylactic acid in a chemical reaction system lactic acid or a mixture of polycondensation or polymerization, application of the "single-nano-metal catalyst" and "nano-metal catalyst" and "nano binary catalyst composition" and so nanoscopic catalyst. “纳米级催化剂”,在乳酸缩聚或聚合反应体系中,具有与同等普通催化剂,更高的催化效率和催化活性及更低的残留量,并且还具有加速促进聚合体系反应的进程、缩短反应时间、降低了物料的消耗、提高了聚乳酸的产收率、催化剂溶入聚合体系均匀和体系添加量减小、聚合体系无污染排放等许多优点。 "Nanoscopic catalyst", at the time of lactic acid polycondensation or polymerization reaction system, the catalyst having the same general, higher catalytic efficiency and lower the catalytic activity and residues, and also having a accelerate the process of promoting the polymerization reaction system, to shorten the reaction , reduces the consumption of materials, to improve the yield of the production of polylactic acid, the catalyst dissolved in the polymerization system uniform system decreases and amount of the polymerization system many advantages polluting emissions.

在本“方案一”中乳酸或乳酸混合物缩聚合成反应体系中,由于首创使用了“热传导介质负压对流排气微波辐射旋转加热技术”,改变了传统加热反应体系的反应步骤和加热顺序,从而也改变了反应体系中,催化剂集中投放的方法和工序。 In the "Program a" lactic acid or a mixture of the polycondensation reaction system, since the first use of the "heat conducting medium vacuum exhaust convection microwave heating technology rotation", changing the sequence of reaction steps conventional heating and the heating of the reaction system, thereby also changed in the reaction system, the catalyst concentration and delivery process step. 为了适合新的缩聚合成反应体系的需要,经过多次实验确定并首先提出,在乳酸或乳酸混合物缩聚合成反应体系中,应用“多步添加”“纳米双金属催化剂”和“纳米单金属催化剂”及“纳米组合二元催化剂”的投放工艺技术方法和添加次序。 In order to fit the new synthesis requires polycondensation reaction system, and after many experiments to determine first proposed, in lactic acid or a mixture of polycondensation reaction system, application of "multi-step add" "nano-metal catalyst" and "single nano-metal catalyst" and "nano binary catalyst composition" technology delivery methods and order of addition. 从而有效的解决了在缩聚合成化学反应体系中,集中投放催化剂易集聚、易结块、易沉淀等降低催化剂的活性,使缩聚合成化学反应速度变慢,反应生成物含催化剂残留过多,增加了反应物提纯的成本,降低了反应物的产收率,产物品质变差等许多弊病。 Thus effectively solves the chemical polycondensation reaction system, the catalyst concentration is easy to assemble delivery, easy to agglomerate, precipitation easily reduced activity of the catalyst, the polycondensation reaction rate of chemical synthesis, the reaction product containing residual catalyst excessive increase the reaction was purified in the cost, the production yield of the reaction was reduced, the product quality deteriorates and many ills. 从而使乳酸或乳酸混合物高效率的缩聚合成高产率的、清洁的聚乳酸。 So that lactic acid or a mixture of high efficient high yield synthesis of condensation, cleaning polylactic acid.

催化剂投放方法一:是将“纳米级催化剂”或常规复合催化剂分为两次或多次顺序加入反应体系中,第一次添加是将“纳米级催化剂”或常规复合催化剂总量的3/5加入经过脱水扩链的高纯度乳酸预缩聚物中,进行预缩聚;第二次添加是在乳酸预缩聚完成后,将乳酸预缩聚产物和剩下的2/5“纳米级催化剂”或常规复合催化剂一起置入“热传导介质负压对流排气微波辐射旋转加热”装置中,经微波辐射加热缩聚合成聚乳酸。 A catalyst delivery method: is "nanoscopic catalyst" or conventional composite catalyst into two or more sequentially added to the reaction system, the first addition is "nanoscopic catalyst" or amount of a conventional catalyst complex 3/5 after addition of the chain extender dehydration high purity lactic acid pre-polycondensate, a pre-polycondensation; after the second addition of acid is complete precondensation, the lactic acid polycondensation product and the rest of the pre 2/5 "nanoscopic catalyst" or conventional composite catalyst together into "convection heat transfer medium vacuum exhaust rotary microwave heating" apparatus, was heated by microwave irradiation polycondensation polylactic acid. 这种多步添加““纳米级催化剂”或常规催化剂的工艺技术方法,能够有效的提高催化剂的效率,又能保持催化剂具有较高的活性,缩短了缩聚反应时间,有效的提高了聚乳酸的产收率和产品的品质及较高的分子量等许多优点。 This multi-step process of adding art methods "" nanoscopic catalyst "or conventional catalysts, can effectively improve the efficiency of the catalyst, while maintaining a high activity catalyst, the polycondensation reaction time is shortened, effectively improve the polylactic acid many production yield and product quality advantages of a higher molecular weight and the like.

催化剂投放方法二:是将“纳米级催化剂”或常规催化剂按顺序加入反应体系中,第一次添加是将“纳米级催化剂”或常规复合催化剂加入经过脱水扩链的高纯度乳酸预缩聚物中,进行预缩聚;第二次添加是在乳酸预缩聚完成后,将乳酸预缩聚产物和“纳米级催化剂”或常规催化剂一起置入“热传导介质负压对流排气微波辐射旋转加热”装置中,经微波辐射加热聚合成聚乳酸。 The catalyst delivery method II: is "nanoscopic catalyst" or a conventional catalyst was sequentially added to the reaction system, the first addition is "nanoscopic catalyst" or conventional composite catalyst was added dehydrated chain high purity lactic acid pre-polycondensate performed precondensation; after the second addition of acid is complete precondensation, the precondensation product, and lactic acid "nanoscopic catalyst" or placed with conventional catalysts "radiant heat transfer medium heated rotary vacuum exhaust convection microwave" means, by microwave irradiation polymerized to polylactic acid. 这种方法是:利用了两性“纳米级催化剂”的脱水性能和催化聚合性能,使脱水扩链乳酸进一步脱水预缩聚成高分子量聚合物,并由聚合物而得到高产率、高性能、高分子量的聚乳酸。 This method is: the use of the amphoteric "nanoscopic catalyst 'dewatering performance and catalytic performance of the polymerization, the chain extender dehydration polycondensation of lactic acid is further dehydrated pre-molecular weight polymer, a polymer obtained by a high yield, high-performance, high molecular weight polylactic acid.

以上所述的两种方法中,通过改变不同组份的催化剂和添加次序,可以组合出许多方法来,这里就不一一列举了。 The two methods described above, by changing the different compositions and order of addition of the catalyst, they may be combined in a number of ways, not list them here.

聚乳酸是近年来发展迅速的易降解的高分子化合物,本发明可在乳酸或乳酸混合物缩聚或聚合过程中随催化剂一同加入金属离子纯化剂MD1024,(用量催化剂∶纯化剂=1∶0.5-2)制备出来的聚乳酸老化性能显著。 The polylactic acid is rapidly growing in recent years, easily degradable polymer compound according to the present invention during the polymerization or polycondensation catalyst is added together with the metal ions in the purifying agent MD1024 lactic acid or mixtures thereof, (the amount of catalyst: purifying agent = 1:0.5-2 ) aging properties of the polylactic acid prepared out significantly.

为了提高聚乳酸的热稳定性和机械性能及相对分子量,本“方法一”采用了扩链剂进行乳酸缩聚低分子量聚乳酸的扩链的方法,使聚乳酸的性能得以大大的提高。 In order to improve the thermal stability of the polylactic acid and the relative molecular weight and mechanical properties, the "method one" chain extender employed method for polycondensation of low molecular weight polylactic acid chain-extended, so that polylactic acid can be greatly improved performance. 使用扩链剂:具有(1)对聚乳酸中活泼的羟端基进行封闭,提高了产物的热稳定性;(2)通过扩链剂引进官能团,可使聚乳酸的机械性能和制造性能得到提高;(3)扩链剂用量少,无许分离等优点。 Chain extender: a (1) of the polylactic acid active hydroxyl end groups be closed, to improve the thermal stability of the product; (2) the introduction of a functional group through the chain extender, can manufacturing performance and mechanical properties of the obtained polylactic acid increase; (3) a chain extender with a small amount, no separate many advantages.

c.热传导介质负压对流排气微波辐射旋转加热技术c.1技术阐述微波能量场促进有机化学体系合成反应技术,是目前迅速发展起来的前沿学科。 C. convection heat transfer medium vacuum exhaust rotary microwave heating technology c.1 techniques are described microwave energy field system promote organic chemical synthesis techniques, it is the rapid development of frontier. 20世纪80年代微波开始在化学领域中得到广泛的研究和利用,并在有机化学合成反应体系中取得了积极的进展和卓有成效的效果,这可以说是化学领域中的一场技术革命。 1980 microwave began to get in the field of chemistry and the use of extensive research, and has made positive progress and fruitful results in synthetic organic chemistry reaction system, it can be said that a technological revolution in the field of chemistry. 微波是指波长为1mm-1m,频率范围为300-300,000MHz,具有穿透性的电磁波,工业上所使用的微波频率为915MHz和2450MHz两个频点。 It refers to a wavelength of the microwave 1mm-1m, the frequency range 300-300,000MHz, penetrating electromagnetic wave having a frequency of the microwave used industrially for two frequencies 915MHz and 2450MHz. 微波在有机化学合成反应中,具有独特的效应和优点,它具有快速升温、体加热、加快反应速度、缩短反应时间、减少副反应、提高反应选择性和产率、节省能源消耗、不污染环境等优点。 Microwave reactions in synthetic organic chemistry, has unique effects and advantages of having a rapid heating, heated to accelerate the reaction rate, shorten the reaction time, reduce side effects, improve the reaction selectivity and yield, saving energy consumption, do not pollute the environment Etc.

目前,国内外学术界一般认为,微波对有机化学合成反应的高效性来自于它对极性物质的热效应。 Currently, academic circles generally believed that microwave efficiency of organic chemical synthesis reaction from thermal effects its polarity substance. 极性分子接受微波辐射能量后,通过分子偶极高速旋转和振动(每秒几亿次至几十亿的极化)而产生内热效应,微波对极性分子的热效应是极其明显的,而与传统的加热方式靠热传导和热对流过程是截然不同的。 After the polar molecules subjected to microwave radiation energy by high-speed rotation and vibration of the molecular dipole (several hundred million to several billion times per second polarization) to generate heat effects, thermal effects of microwave polar molecules is extremely significant, and with conventional heating by conduction and convection heat process is different. 极性分子的介电常数较大,同微波有较强的耦合作用,非极性分子同微波不产生或产生较弱的耦合作用。 Polar molecules larger dielectric constant, a microwave with a strong coupling, non-polar molecules no or weak coupling with the microwave. 在常见的物质中,铁磁性金属和金属导体因吸收和反射微波而用于屏蔽微波辐射。 In a common material, ferromagnetic metals and metal conductor due to absorption and reflection of microwaves for shielding microwave radiation. 玻璃、陶瓷等能透过微波,本身几乎不产生热效应,因而可以用于制造反应器的材料,大多数有机化合物和含水物质、极性无机盐类等能很好的吸收微波,这些性能和特点为微波辐射技术,能顺利的进入有机化学合成领域奠定了坚实的基础。 Glass and ceramics can, itself hardly generated through thermal effects of microwave, it is possible to manufacture the material for the reactor, most organic compounds and an aqueous material, inorganic salts polarity can well absorb microwaves, these performance characteristics, and microwave radiation technology, can smoothly into the field of synthetic organic chemistry and laid a solid foundation.

微波技术成功的应用于有机化学合成反应,使传统有机化学合成反应速度提高了数倍,数百倍甚至上千倍。 Microwave technology successfully used in organic chemical synthesis, traditional synthetic organic chemistry reaction rate increased by several times, several hundred or even thousands of times. 但是微波技术应用在乳酸有机合成聚乳酸反应体系中,还仅仅是一个起步阶段。 However, application of microwave technology in organic synthesis polylactic acid in the reaction system, is just an early stage. 有文献报道,用惰性气体保护丙交酯微波加热化学聚合成聚乳酸的报道,但是到迄今为止该项技术上未达到工业化生产,仍在实验室阶段中,原因是该项技术在聚合反应体系中,减压操作比较困难,充入保护气体也很不方便,成本较高等等,而无法达到工业化要求。 Has been reported that the microwave heating chemical polymerization of lactide into polylactic acid with inert gas propan reported, but to date this technology has not reached the industrial production, is still in the laboratory stage, because the technology in the polymerization reaction system , the pressure reducing operation is difficult, the protective gas filling inconvenient, high costs, etc., can not achieve the requirements of industrialization.

乳酸低聚物和聚合单体丙交酯,属于非极性结晶体,对微波辐射能量吸收较差,直接应用微波辐射能量进行加热聚合,其效果不十分理想,反而会造成聚合体系加热不均、聚合时间过长、耗能大、物料损失过多、聚合产物品质变差、聚合产物分子量低等等,而带来的许多弊病。 Lactic acid oligomers and polymerizable monomers lactide, nonpolar crystalline, poorly absorbed microwave radiation energy, direct application of microwave energy for heating the polymerization, the effect is not very good, it will cause uneven heating of the polymerization system, polymerization time is too long, energy consumption, excessive material loss, deterioration of the quality of the polymerization product, the polymerization product of low molecular weight, etc., brought many ills. 为了解决乳酸和乳酸低聚物及聚合单体丙交酯,不适宜应用微波辐射直接聚合或缩聚加热及乳酸脱水蒸气散发等问题,经过多方思考和查阅大量有关资料及经过多次研究决定,利用强吸收微波物质经微波辐射激发而产热的原理和空气对流排气等原理,给乳酸低聚物和聚合单体丙交酯间接加热及强制空气对流排出乳酸脱水体系的水份,这也就是本发明的“热传导介质负压对流排气微波辐射旋转加热”技术。 In order to solve the lactic acid and lactic acid oligomers and polymerizable monomers lactide, inappropriate application of microwave heating direct radiation polymerization or polycondensation distributing steam and lactate dehydrogenase problems after careful consideration and inspection lot information and decide after several studies using strong absorption of microwave radiation microwave excitation principle material and a heat exhaust air convection principle and the like, to lactic acid oligomers and polymerizable monomers lactide indirect heating and forced air convection system discharging moisture dehydration of lactic acid, which is the present invention "heat conducting medium vacuum exhaust convection heating microwave radiation rotation" technique.

c.2“热传导介质负压对流排气微波辐射旋转间接加热”原理许多有机反应物不能直接明显地吸收微波能(如:乳酸低聚物和聚合单体丙交酯等有机物),但是将微波场能辐射到含有某种“高吸收微波物质”的表面上,由于“高吸收微波物质”表面和内部分子与微波场能的强烈作用,微波能将被转变热,从而使“高吸收微波物质”被很快加热至很高的温度。 C.2 "convection heat transfer medium vacuum exhaust rotary indirect heating microwave radiation" principle many organic reactant does not significantly absorb microwave energy directly (such as: lactic acid oligomers and polymerizable organic monomer such as lactide), but the microwave field energy irradiated onto the surface containing the certain "high microwave absorbing substance" due to "the high microwave absorbing substance" strongly interact with the surface and inside the microwave field energy of molecules, can be converted microwave heat, so that "high microwave absorption material "it is rapidly heated to a high temperature. 尽管反应器中的反应物料不会被微波能直接加热,但当反应物料经反应器与受微波激发的“高吸收微波物质”接触时,“高吸收微波物质”将自身的热通过反应器传递给反应物料中,使反应物料的温度迅速升高而达到所需自身聚合的温度,从而完成了“热传导介质微波辐射间接加热”的过程。 While the reaction mass in the reactor is not heated directly by the microwave energy, but over time the reaction mass reactor by microwave excitation of a "high microwave absorbing substance" in contact with "high microwave absorbing substance" itself of heat transfer through the reactor to the reaction mass, the temperature of the reaction mass rises rapidly to reach the desired polymerization temperature itself, thereby completing the process of "indirect heat transfer medium microwave heating".

热传导介质负压对流排气微波加热乳酸脱水系统:是利用微波内部加热特点和抽风机形成负压对流,使滤饼内外产生压力梯度排出乳酸中脱水蒸气水份达到加速乳酸脱水的目的。 Convection heat transfer medium vacuum exhaust system of the microwave heating dehydration of lactic acid: internal heating using a microwave features and a negative pressure blower convection, a pressure gradient inside and outside the cake discharging object water vapor removal lactic acid reaches the acceleration of dehydration. 脱水设备的抽风系统一方面可以对流带走水份,另一方面使脱水系统形成负压防止乳酸在高温下,产生的酸性气体的散逸。 Ventilation systems on the one hand dewatering equipment convection away moisture, on the other hand a negative pressure to prevent dehydration system dissipating lactic acid gas at high temperature produced.

c.3“热传导介质”的选取作为热传导介质强吸收微波的物质很多,有铁磁性物质,变价元素的金属氧化物,纤维性物质和碳化物等物质。 Many substances c.3 select "heat conducting medium" as a heat conduction medium strong absorption of microwaves, ferromagnetic substance, a metal oxide of a trivalent element becomes, fibrous material and carbide materials. 铁磁性物质,具有很强的微波吸收能力,在微波场中强烈吸收微波而被加热,具有升温速度快、传热性能好等特点。 Ferromagnetic substance, a strong microwave absorption capacity, strongly absorb microwave in a microwave field and are heated, having heating speed, good heat transfer performance characteristics. 但是铁磁性物质,在超过100℃以上本体吸收微波效率变差、性能不稳定等因素而不能胜任作为该项技术的“热传导介质”;变价元素的金属氧化物,在强微波场中易分解,也不适合作为“热传导介质”;碳化物,是良好的微波吸收材料。 However, ferromagnetic materials, or more than 100 ℃ microwave absorption efficiency deteriorates body, unstable factors such as the technique can not do "heat conducting medium"; a metal oxide of a divalent element becomes easily decomposed in a strong microwave field, not suitable as a "heat conducting medium"; carbide is a good microwave absorbing material. 在碳化物族中,活性碳具有很强的微波吸收性能,但是作为“热传导介质”,它在微波场加热中会产生火化,温度升高太快,并且温度很高难以控制,也不适合作为“热传导介质”;碳化硅(Sic)是一种强吸收微波物质,在微波场中吸收微波而被加热,且具有升温速度快,传热性能好,并且在一定温度范围内能保持性能稳定,而不会出现热失控现象,可以反复使用,是作为该项技术最佳的“热传导介质”首选材料之一。 Family carbide, activated carbon has strong microwave absorbing properties, but as a "heat conducting medium", which produces spark in a microwave heating field, the temperature rises too fast, and a high temperature is difficult to control, are not suitable for "heat conducting medium"; silicon carbide (Sic) is a strong microwave absorbing material absorbing microwaves in the microwave field and are heated, and having a heating speed, good heat transfer performance, and can maintain stable performance in a certain temperature range, without thermal runaway phenomenon, it can be used repeatedly, as the technology is one of the best "heat transfer medium" material of choice. 所以本发明选用碳化硅作为“热传导介质”或耗散物质作为热传导介质。 Therefore, the present invention is the choice of silicon carbide as "heat conducting medium" or dissipative material as a heat transfer medium.

c.4“热传导介质”的使用方法“热传导介质”碳化硅(Sic)在乳酸有机化学合成体系中,一般有三种间接传热的使用方法:第一种方法:将碳化硅颗粒或粉末,直接均匀的铺垫在微波加热器内陶瓷托盘或耐烧玻璃托盘上,在将盛有乳酸低聚物或聚合单体丙交酯的反应器放在铺有碳化硅的托盘上,进行微波辐射加热,这时碳化硅首先被微波加热,被加热了的碳化硅,通过反应器的底部把热均匀的传递给缩聚或聚合源料乳酸低聚物或聚合单体丙交酯中,这时缩聚或聚合源料乳酸低聚物或聚合单体丙交酯汇集了两个途径来的热量(一个是来自碳化硅传导的热量,一个是来自微波直接辐射产生的热量)同时加热,进行缩聚或聚合成聚乳酸,从而完成了″热传导介质微波辐射加热″过成。 C.4 "heat conducting medium" in use "heat conducting medium" silicon carbide (Sic) lactic acid in organic chemical synthesis system, there are generally three methods using indirect heat transfer: The first method: the silicon carbide particles or powder, directly bedding uniform ceramic tray in the microwave heater or fire-resistant glass tray filled with lactic acid in the oligomeric or polymeric ester monomers lactide reactor is placed on a tray covered with silicon carbide, microwave radiation heating, microwave heating time is first silicon carbide, silicon carbide is heated, the bottom of the reactor through the uniform transfer of heat to a source material polycondensation or polymerization of the polymerizable monomer or oligomer of lactic acid lactide, polycondensation or polymerization time source material lactic acid oligomers lactide or polymerizable monomers brings together two ways to the heat (a heat is conducted from a carbide, a microwave heat is generated from the direct radiation) while heating, polycondensation or polymerization into poly lactic acid, thus completing the "heat conducting medium microwave radiant heating" over to. 该方法简单而且实用,并通过调节碳化硅铺设量或调节微波功率,可得到不同的平衡温度。 The method is simple and practical, and by adjusting the amount of silicon carbide or laying adjusting microwave power, different equilibrium temperatures is obtained.

第二种方法:将碳化硅颗粒或粉末和TTZF型高温粘合剂(也可用其它类型的高温粘合剂),按3比1的比例进行混合均匀,然后均匀的涂抹在耐烧玻璃反应器或陶瓷反应器有效装载部位以下反应器外部和底部,涂抹厚度试反应器大小和反应聚合所需温度而定(一般实验室反应装置涂0.1mm-5mm厚度左右既可),涂抹均匀并固化稍后干燥完成后,在用耐高温纤维涂抹TTZF型高温粘合剂,捆粘在上次涂抹的碳化硅表面(这一工序是防止碳化硅在高温下脱落,影响聚合体系的热效率),待粘合剂干燥后,将反应器装入适当的水或其它溶剂放入微波加热装置中,进行缓慢提高微波功率到1000W进行加热30min,加热完成后,取出反应器待冷却后,再涂抹一层TTZF型粘合剂干燥后即可以加热使用了。 The second method: the silicon carbide particles or powder and high-temperature adhesive TTZF (may also be other types of high temperature adhesive), according to Comparative Example 3 were mixed uniformly to 1, and then spread evenly fire-resistant glass reactor efficient loading or ceramic reactor outside the reactor and the bottom portion, the thickness of the applied pilot reactor size required for the polymerization reaction and temperature-dependent (general laboratory reactor coating thickness of about 5mm 0.1mm-can), spread evenly and slightly cured after completion of the drying, the high-temperature adhesive applicator TTZF with high temperature resistant fibers, silicon carbide surface adhered to the bundle of the last applied (this step is to prevent the shedding of silicon carbide at high temperature, affecting the thermal efficiency of the polymerization system), to be glued after the mixture was dried, the reactor was charged with water or other suitable solvent into a microwave heating apparatus, to be slowly increased microwave power 1000W heated 30min, after heating is completed, remove the reactor after cooling, and then apply a layer of TTZF drying adhesive may be heated after use. 加热过程和第一种方法基本相同。 And a first heating process is basically the same. 该方法间接加热性和均匀性优于第一种方法,并且该制作方法简单、易于制作、调节微波输出功率可得到不同的平衡温度。 A first method and the indirect heating method is superior uniformity, and the production method is simple, easy to manufacture, adjusting the microwave output different equilibrium temperatures is obtained. 本方法和加热过程,具有乳酸脱水、预缩聚、缩聚或聚合容为一体的功效,较复合实验室和化工工业清洁生产使用。 The present method and heating, dehydrating with lactic acid, precondensation, polycondensation or polymerization vessel as one of the efficacy, than the composite laboratory and industrial cleaning chemical production and use.

第三种方法:在制造微波场辐射聚合反应器时,将碳化硅粉粒或粉末,经由3比1的比例与TTZF型粘合剂混合均匀后(这项工序主要是使导热夹层与反应器内外壁紧密相连,浑为一体,更具有耐冲击性和传热性。本工序也可以不用,粘合剂也可以使用其它类型的高温粘合剂和热传导介质),嵌入所制造的耐烧玻璃反应器或陶瓷反应器的有效加载以下,反应器外部和底部内外层之间,构成碳化硅热传导反应器热传导介质中间夹层。 The third method: during the production of the microwave field radiation polymerization reactor, or the silicon carbide powder particles, the ratio of 3 to 1 by the binder uniformly mixed with TTZF type (mainly the heat conducting step sandwich reactor inner and outer walls are closely linked, muddy as a whole, having more impact resistance and heat resistance. this step may be practiced without adhesive may also be other types of high-temperature heat transfer medium and the adhesive), embedded resistant glass manufactured burn effective loading of the reactor below or ceramic reactor, outside the reactor between the inner and outer layer and a bottom, the silicon carbide constituting the thermally conductive medium thermally conductive reactor mid sole. 热传导介质夹层厚度试反应器大小和反应聚合所需温度而定,用这种方法制造出来的反应器和热传导系统浑为一体,更具有其实用性和标准性。 The thickness of the interlayer heat transfer medium sized pilot reactor and the desired polymerization reaction temperature, are manufactured by such a reactor and a heat transfer system muddy as a whole, with its more practical and normative. 该方法具有热传导效率高,加热均匀,反应器操作简单,清洁,适合标准化生产,更具有原料脱水浓缩、缩聚或聚合等一体化的功效,调节微波输出功率可得到不同的平衡温度,微波加热方式与前两例基本相同。 This method has the effect of high heat transfer efficiency, uniform heating, reactor operation is simple, clean and suitable for standardization of the production, the raw material is more concentrated dehydration, polymerization, condensation, or integration, different regulating microwave output obtained equilibrium temperature, microwave heating substantially the same as the previous two cases. 这种一体化反应器正适合当今清洁生产的使用要求。 Such reactors are suitable for integration in today's cleaner production requirements.

3.乳酸两种工艺技术路线直接缩聚合成聚乳酸的方法第一种乳酸缩聚合成聚乳酸工艺技术路线说明方法一:乳酸脱水处理:乳酸脱水处理可采用常规加热减压或常压除水工艺,即控制适当的真空度和温度及扩链剂的条件下,进行减压或常压除去乳酸中的水份,并且对乳酸脱水低聚物进行预扩链。 3. The two kinds of lactic acid direct polycondensation route technology polylactic acid first method for synthesizing polylactic acid polycondensation technology described method a route: dehydrated lactic acid: lactic acid is dehydrated using conventional heat treatment under reduced pressure or normal pressure dewatering process, i.e. control of appropriate conditions of temperature and degree of vacuum and a chain extender under reduced pressure or atmospheric moisture to remove lactic acid and oligomers of lactic acid is dehydrated pre chain. 常规加热除水温度为80-120℃,真空度为10-110mmHg,脱水时间为120min。 In addition to conventional heating water temperature is 80-120 ℃, vacuum degree of 10-110mmHg, dewatering time is 120min. 若在常规加热减压或常压脱水处理过程中,使用搅拌器辅助搅动物料,可提高除水效率。 When the heating in a conventional atmospheric or reduced pressure dehydration process, agitating using an agitator auxiliary materials, the water removal efficiency can be improved.

预缩聚:以脱水扩链乳酸低聚物为原料,在常规加热和两性“纳米级催化剂”的催化下,进行减压或常压扩链乳酸低聚物脱水预缩聚。 Precondensation: dehydrated chain lactic acid oligomer as a raw material, in the conventional heating and catalytic amphoteric "nanoscale catalyst", under reduced pressure or atmospheric chain lactic acid oligomers pre-dehydration polycondensation. 预缩聚温度为90-160℃,缩聚过程中采用从低温缓慢升至到高温的方法,以防止缩聚过程中乳酸低聚物原料损耗过多和防止预缩聚产物碳化。 Precondensation temperature of 90-160 deg.] C, slowly raised from low to high temperatures employed during the polycondensation process, to prevent the polycondensation process of lactic acid oligomer feed to prevent excessive loss of the pre-polycondensation product and carbonized. 预缩聚真空度10-110mmHg,预缩聚时间为300min。 Precondensation vacuum degree 10-110mmHg, precondensation time is 300min.

缩聚合:在″纳米级催化剂″的存在下,以乳酸预缩聚物为原料“热传导介质负压对流排气微波辐射旋转加热”常压缩聚,缩聚微波功率为50-500W,缩聚时间为10-28min。 Polycondensation: in the presence of "nanoscopic catalyst" to lactic acid as a raw material precondensate "convection heat transfer medium vacuum exhaust rotary microwave heating" compressed normally polyethylene, polycondensation microwave power 50-500W, polycondensation time of 10 to 28min.

实施例一将150g纯度为85%的L-乳酸和扩链剂0.1-0.26g的二异氰酸酯一起,加入到带有搅拌器的500ml三颈烧瓶中,充分搅拌均匀后加热,体系温度达到100℃开始抽真空,在真空度为60-100mmHg的条件下搅拌脱水预扩链120min。 Example 150g of a purity of 85% lactic acid and L- chain extender diisocyanate 0.1-0.26g together, added to 500ml three-necked flask equipped with a stirrer, stir evenly heating temperature in the system reached 100 ℃ start the vacuum, a vacuum degree of dehydration under stirring 60-100mmHg pre chain 120min. 脱水完成后,反应体系从100℃缓慢升温到140℃,加入0.3-0.6g两性″纳米级氧化锌与三氧化二镧″组成的纳米双金属催化剂(按质量比1∶0.06--0.2,催化剂用量与单体的质量比为1∶100-4000)的催化和真空度40-80mmHg条件下,继续脱水扩链预缩聚210-300min。 After completion of the dehydration, the reaction system was gradually raised from 100 deg.] C to 140 deg.] C, was added 0.3-0.6g amphoteric "nano zinc oxide and lanthanum oxide" nano-metal catalyst composition (mass ratio 1:0.06--0.2 catalyst under a vacuum of 40-80mmHg conditions and catalytic amount of the monomer mass ratio 1:100-4000), the dehydration continues chain prepolycondensation 210-300min. 预缩聚完成后,将预缩聚产物取出,装入外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中,再加入0.06-1g“纳米级辛酸亚锡”催化剂后,用薄膜密封好烧杯口放入微波加热炉中,在调节微波输出功率为50-500W的条件下,进行缩聚10-28min,即得透明物体聚乳酸(PLA)。 After the completion of the precondensation, the precondensation product is withdrawn, and the bottom layer was charged in a beaker containing a silicon carbide coating applicator "heat conducting medium", and then added 0.06-1g "nanoscale stannous octoate" catalyst, sealed with a film mouth beaker placed in a microwave oven under microwave conditions regulating the output power of 50-500W, polycondensation 10-28min, to obtain a transparent object of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.3-1.6g“纳米级氧化锌”及0.1-0.26g二异氰酸酯与季戊四醇(按质量比1∶0.2-1)组合的双扩链剂一起,加入到带有搅拌器的500ml三颈烧瓶中,充分搅拌均匀后加热,反应体系温度达到100℃时开始抽真空,在真空度为60-100mmHg的条件下搅拌脱水预扩链120min。 Example Two 150g of 85% pure lactic acid, and DL- of 0.3-1.6g "nano zinc oxide" and 0.1-0.26g diisocyanate along with a chain extender agent is pentaerythritol bis (mass ratio 1:0.2-1) combined embodiment , was added to a 500ml three-necked flask equipped with a stirrer, stirred sufficiently uniform heating, the vacuum is the reaction temperature of the system reached 100 deg.] C, stirred at a vacuum degree of dehydration of the pre-conditions 60-100mmHg chain 120min. 脱水完成后,体系从100℃缓慢升温到140℃,加入0.2-0.8g两性“纳米级氧化锌与三氧化二锑”组成的纳米双金属催化剂(按质量比1∶0.06-0.30,催化剂用量与单体的质量比为1∶100-4000)的催化和真空度为40-80mmHg的条件下,继续脱水扩链预缩聚210-300min。 After completion of the dehydration, the system was slowly raised from 100 deg.] C to 140 deg.] C, was added 0.2-0.8g amphoteric "nano zinc oxide and antimony trioxide" nano-metal catalyst consisting of bis (1:0.06-0.30 mass ratio, amount of catalyst and the mass ratio of monomers 1:100-4000) and the degree of vacuum of 40-80mmHg catalytic conditions, dehydration continues chain prepolycondensation 210-300min. 预缩聚完成后,将预缩聚产物取出,装入外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中,再加入0.06-1g“纳米级辛酸亚锡”催化剂后,用薄膜密封好烧杯口放入微波加热炉中,在调节微波输出功率为50-500的条件下,进行缩聚10-28min,即得透明物体聚乳酸(PLA)。 After the completion of the precondensation, the precondensation product is withdrawn, and the bottom layer was charged in a beaker containing a silicon carbide coating applicator "heat conducting medium", and then added 0.06-1g "nanoscale stannous octoate" catalyst, sealed with a film mouth beaker placed in a microwave oven, at 50 to 500 adjust the microwave output polycondensation 10-28min, to obtain a transparent object of polylactic acid (PLA).

以上方法一中的两例可通过改变“纳米级催化剂”和添加次序,就可以组合出许多形式的缩聚合成体系,这里就不一一例举了。 A method of the above two cases can be obtained by changing the "nanoscopic catalyst" and the order of addition, the compositions can be in many forms polycondensation system, here it is not exemplified.

方法二:乳酸脱水处理:乳酸脱水处理可采用“热传导介质负压对流排气微波辐射旋转加热”常压或“热传导介质微波辐射加热”真空除水工艺,即控制适当的“热传导介质负压对流排气微波辐射旋转加热”的输出功率和脱水催化剂及扩链剂的条件下,进行常压或真空除去乳酸中的水份,并且对乳酸脱水低聚物进行预扩链,除水功率为50W-1000W,脱水时间为20-100min。 Method two: dehydrated lactic acid: lactic acid can be dehydrated "convection heat transfer medium vacuum exhaust rotary microwave heating" normal or "heat conducting medium microwave radiant heating" process water removed in vacuo, i.e. the control of appropriate "convection heat transfer medium underpressure output power condition of the dehydration catalyst and a chain extender and an exhaust rotary microwave heating ", was subjected to atmospheric moisture or lactic acid is removed in vacuo, and oligomers of lactic acid is dehydrated pre chain, in addition to water power of 50W -1000W, dehydration time 20-100min.

预缩聚:以脱水扩链乳酸低聚物为原料,在“热传导介质负压对流排气微波辐射旋转加热”和两性“纳米级催化剂”的催化下,进行常压或真空扩链乳酸低聚物继续脱水预缩聚,预缩聚功率为50-520W,缩聚过程中采用从低功率输出缓慢升至高功率输出的方法,以防止缩聚过程中乳酸低聚物原料损耗过多和防止预缩聚产物碳化,预缩聚时间为28-110min。 Precondensation: dehydrated chain lactic acid oligomers as starting material, under catalytic "convection heat transfer medium vacuum exhaust rotary microwave heating" and gender "nanoscale catalyst", for atmospheric or vacuum chain lactic acid oligomers the dehydration continues precondensation, precondensation power of 50-520W, the method was slowly increased from a low power output of a high power output used in the process of the polycondensation, during the polycondensation to prevent lactic acid oligomer feed to prevent excessive loss of the pre-polycondensation product and carbonizing the pre condensation time 28-110min.

缩聚合:在“纳米级催化剂”的存在下,以乳酸预缩聚物为原料“热传介质负压对流排气微波辐射旋转加热”常压缩聚,缩聚微波输出功率为50-500W,缩聚时间为10-28min。 Polycondensation: in the presence of "nanoscopic catalyst" to lactic acid as a raw material precondensate "convection heat transfer medium vacuum exhaust rotary microwave heating" compressed normally polyethylene, polycondensation microwave output of 50-500W, the polycondensation time 10-28min.

实施例一将150g纯度为85%的L-乳酸和0.1--0.26g的二异氰酸酯一起,加入到500ml外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中。 Example 150g of a 85% purity of L- lactic acid and diisocyanate 0.1--0.26g together, added to the bottom of the outer layer and the smear 500ml "heat conducting medium" beaker silicon carbide coating. 充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波输出功率缓慢调节升高至50-450W下,加热脱水预扩链20-100min。 After stir, a microwave oven with a rotating radiation into the convection vacuum exhaust system, the microwave output adjusted slowly raised to at 50-450W, the pre-heat dehydration chain 20-100min. 乳酸脱水预扩链完成后,将微波输出功率缓慢调节升高至50-480W,加入0.3-0.6g两性“纳米级氧化锌与三氧化二镧”组成的纳米双金属催化剂的催化下,继续脱水扩链预缩聚28-110min。 Catalytic metal catalyst nano-lactic acid is dehydrated after completion of the pre-chain, slowly adjust the microwave output raised to 50-480W, amphoteric added 0.3-0.6g "nano zinc oxide with lanthanum oxide," consisting of dehydration continues chain precondensation 28-110min. 预缩聚完成后,加入0.06--1g“纳米级辛酸亚锡”催化剂后,用薄膜密封好烧杯口放回微波加热炉中,调节微波输出功率为50-500W,缩聚10-28min,即得透明物体聚乳酸(PLA)。 After completion of the pre-polycondensation, after adding 0.06--1g "nanoscale stannous octoate" catalyst, the beaker opening sealed with a film back into the microwave oven, the microwave output power regulating 50-500W, polycondensation 10-28min, to obtain a transparent objects of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.3-1.6g“纳米级氧化锌”及0.1-0.26g二异氰酸酯与季戊四醇(按质量比1∶0.2-1)组合的双扩链剂一起,加入到500ml外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中。 Example Two 150g of 85% pure lactic acid, and DL- of 0.3-1.6g "nano zinc oxide" and 0.1-0.26g diisocyanate along with a chain extender agent is pentaerythritol bis (mass ratio 1:0.2-1) combined embodiment , was added to a 500ml beaker and the smear layer and bottom "heat conducting medium" silicon carbide coating. 充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波输出功率缓慢调节升高至50-450W下,加热脱水预扩链20-100min。 After stir, a microwave oven with a rotating radiation into the convection vacuum exhaust system, the microwave output adjusted slowly raised to at 50-450W, the pre-heat dehydration chain 20-100min. 乳酸脱水预扩链完成后,将微波输出功率缓慢调节升高至50-480W,加入0.2-0.8g两性“纳米级氧化锌与三氧化二锑”组成的双金属复合催化剂的催化下,继续脱水扩链预缩聚28-110min。 Pre-chain acid dehydration is completed, the microwave output adjusted slowly raised to 50-480W, amphoteric 0.2-0.8g added a catalytic composite bimetallic catalyst composition "nano zinc oxide and antimony trioxide", to continue the dehydration chain precondensation 28-110min. 预缩聚完成后,加入0.06-1g“纳米级辛酸亚锡”催化剂后,用薄膜密封好烧杯口放回微波加热炉中,调节微波输出功率为50-500W,缩聚10-28min,即得透明物体聚乳酸(PLA)。 After completion of the pre-polycondensation, after addition of 0.06-1g "nanoscale stannous octoate" catalyst, the beaker opening sealed with a film back into the microwave oven, the microwave output power regulating 50-500W, polycondensation 10-28min, to obtain a transparent object polylactic acid (PLA).

以上方法二中的两例可通过改变“纳米级复催化剂”和添加次序,就可以组合出许多形式的缩聚合成体系,这里就不一一例举了。 Method II above two cases by changing the "nano complex catalyst" and the order of addition, the compositions can be in many forms polycondensation system, here it is not exemplified.

第二种乳酸缩聚合成聚乳酸工艺技术路线说明方法一:本方法一是由乳酸在扩链剂和“纳米组合二元催化剂”的存在下,经两种热源(常规加热和热传导介质负压对流排气微波辐射旋转加热)加热,分“多步添加”“纳米组合二元催化剂”的方法,减压和常压下,于100-190℃和输出功率为50-500W,真空度为10-100mmHg和常压的条件下,脱水缩聚540min,得聚乳酸粗品,粗品经精制干燥后得纯净的聚乳酸。 The second polylactic acid polycondensation technology route described method: The first method is by the acid in the presence of chain extenders and "nano binary catalyst composition", and by two kinds of heat sources (conventional heating and convection heat transfer medium underpressure microwave heating exhaust rotation) heating points "multi-step add" method "nano binary catalyst composition", and under normal pressure and reduced pressure, at 100-190 deg.] C and an output power of 50-500W, the degree of vacuum of 10- 100mmHg and atmospheric conditions, dehydration condensation 540min, to obtain a crude product of polylactic acid, the crude product was purified and dried to give the pure polylactic acid.

实施例一将150g纯度为85%的L-乳酸和0.1-0.26g的二异氰酸酯及0.12-0.4g的“纳米级辛酸亚锡与对甲基苯磺酸”(按质量比1∶0.1-1.6)组合二元催化剂一起,加入到带有搅拌器的500ml三颈烧瓶中,充分搅拌均匀后,加热缓慢升温至100-190℃,真空度为50-100mmHg的条件下,脱水扩链缩聚300-480min。 Example 150g of a 85% purity of L- lactic acid and a diisocyanate and 0.12-0.4g of 0.1-0.26g "nanoscale stannous octoate and p-toluenesulfonic acid" (mass ratio 1:0.1-1.6 under) in combination with binary catalyst, was added to a 500ml three-necked flask equipped with a stirrer, was sufficiently stir, heated slowly warmed to 100-190 deg.] C, vacuum degree of 50-100mmHg conditions, dehydration condensation chain 300 480min. 脱水缩聚完成后,将缩聚产物取出,装入外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中,再加入0.08--0.3g“纳米级辛酸亚锡与对甲基苯磺酸”组合二元催化剂后,用薄膜密封好烧杯口放入微波加热炉中,在微波输出功率为50-500W的条件下,继续缩聚10-30min,即得透明物体聚乳酸(PLA)。 After completion of dehydration polycondensation, the polycondensation product was taken out, and the bottom layer was charged in a beaker containing a silicon carbide coating applicator "heat conducting medium", and then added 0.08--0.3g "nanoscale stannous octoate and p-toluenesulfonic acid "after the binary catalyst composition, with a film mouth sealed beaker placed in a microwave oven, the microwave output power of 50-500W conditions, to continue the polycondensation 10-30min, to obtain a transparent object of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.1-0.3g的二异氰酸酯与季戊四醇(按质量比1∶0.2-1)组合的双扩链剂及0.48-1.2g“纳米级乳酸锌与对甲基苯磺酸”(按质量比1∶0.1-2)组合的二元催化剂一起,加入到带有搅拌器的500ml三颈烧瓶中,充分搅拌均匀后,加热缓慢升温至100-190℃,真空度为50--100mmHg的条件下,脱水扩链缩聚300-480min。 Double chain agent 0.48-1.2g "Example Two 150g of 85% pure lactic acid and DL- 0.1-0.3g of the diisocyanate with pentaerythritol embodiment (1:0.2-1 mass ratio) in combination with nano zinc lactate with p-toluenesulfonic acid "binary catalyst (1:0.1-2 mass ratio) in combination, were added to a 500ml three-necked flask equipped with a stirrer, was sufficiently stir, heated slowly warmed to 100-190 deg.] C under a vacuum degree of 50--100mmHg conditions, dehydration condensation chain 300-480min. 脱水缩聚完成后,将缩聚产物取出,装入外层和底部涂料有“热传导介质”碳化硅涂层的烧杯中,再及入0.32--0.8g“纳米级乳酸锌与对甲基苯磺酸”组合二元催化剂后,用薄膜密封好烧杯口放入微波加热炉中,在微波输出功率为50-500W的条件下,继续缩聚10-30min,即得透明物体聚乳酸(PLA)。 After completion of dehydration polycondensation, the polycondensation product was taken out, and charged with an outer layer coating the bottom of the beaker with a silicon carbide coating "heat conducting medium", and then into and 0.32--0.8g "nano zinc lactate and p-toluenesulfonic acid "after the binary catalyst composition, with a film mouth sealed beaker placed in a microwave oven, the microwave output power of 50-500W conditions, to continue the polycondensation 10-30min, to obtain a transparent object of polylactic acid (PLA).

方法二是由乳酸在扩链剂和“纳米组合二元催化剂”的存在下,经“热传导介质负压对流排气微波辐射旋转加热”分“多步添加”“纳米组合二元催化剂”的方法,在常压下,于微波输出功率为50-500W,的条件下,脱水缩聚30-120min,再一次添加“纳米级组合二元催化剂”,于微波输出功率为50-750W,继续缩聚10-30min,得聚乳酸粗品,粗品经精制干燥后得纯净的聚乳酸。 Second, the method of lactic acid in the presence of chain extenders and "nano binary catalyst composition," and by the "radiation heat transfer medium heated rotary vacuum exhaust convection microwave" minute "multi-step add" method "nano binary catalyst composition" in at atmospheric pressure, at a microwave output power of 50-500W, conditions, dehydration condensation 30-120 min, then add a "nano binary catalyst composition", the microwave output power 50-750W, to continue the polycondensation 10- 30min, to obtain a crude product of polylactic acid, the crude product was purified and dried to give the pure polylactic acid.

实施例一将150g纯度为85%的L-乳酸和0.1-0.26g的二异氰酸酯及0.12-0.4g的“纳米级辛酸亚锡与对甲基苯磺酸”(按质量比1∶0.1-1.6)组合二元催化剂一起,加入外层和底部涂抹有“热传导介质”碳化硅涂层的烧杯中。 Example 150g of a 85% purity of L- lactic acid and a diisocyanate and 0.12-0.4g of 0.1-0.26g "nanoscale stannous octoate and p-toluenesulfonic acid" (mass ratio 1:0.1-1.6 ) in combination with the binary catalyst was added and a bottom layer of silicon carbide coatings applied in a beaker of "heat conducting medium" in. 充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波输出功率缓慢调节升高至50-500W,在常压条件下,脱水扩链缩聚60-120min。 After stir, a microwave oven with a rotating radiation into the convection vacuum exhaust system, the microwave output adjusted slowly raised to 50-500W, under atmospheric conditions, dehydration condensation chain 60-120min. 脱水缩聚完成后,再加入0.08-0.3g的“纳米级辛酸亚锡与对甲基磺酸”组合催化剂后,用薄膜密封好烧杯口放回微波加热炉中,在微波输出功率为50-550W,继续缩聚10-30min,即得透明物质聚乳酸(PLA)。 After dehydration polycondensation is completed, added 0.08-0.3g "nano-level of stannous octoate methanesulfonate" After the catalyst composition, the beaker opening sealed with a film back into the microwave oven, the microwave output power of 50-550W , polycondensation continues 10-30min, to obtain a transparent material of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.1-0.3g的二异氰酸酯与季戊四醇(按质量比1∶0.2-1)组合的双扩链剂及0.48-1.2g的纳米级乳酸锌与对甲基苯磺酸(按质量比1∶0.1-2)组合的二元催化剂一起,加入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中。 Double chain according to a second agent to 150g of 85% pure lactic acid and DL- 0.1-0.3g of a diisocyanate with pentaerythritol embodiment (mass ratio 1:0.2-1) combined nanoscale zinc lactate and 0.48-1.2g (1:0.1-2 mass ratio) in combination with the binary catalyst p-toluenesulfonic acid, and added to the outer bottom beaker applicator thermally conductive medium silicon carbide coating. 充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波输出功率缓慢调节升高至50-500W,在常压条件下,脱水扩链缩聚60-120min。 After stir, a microwave oven with a rotating radiation into the convection vacuum exhaust system, the microwave output adjusted slowly raised to 50-500W, under atmospheric conditions, dehydration condensation chain 60-120min. 脱水缩聚完成后,再加入0.32-0.8g的纳米级乳酸锌与对甲基苯磺酸组合的二元催化剂后,用薄膜密封好烧杯口放回微波加热炉中,在微波输出功率为50-550W,继续缩聚10-30min,即得透明物体聚乳酸(PLA)。 After completion of dehydration polycondensation, and then after addition of nanoscale zinc lactate 0.32-0.8g binary catalyst and p-toluenesulfonic acid in combination with a film mouth of the beaker back into sealed microwave oven, the microwave output power 50 550W, polycondensation continues 10-30min, to obtain a transparent object of polylactic acid (PLA).

方案二(属两步聚合)乳酸或乳酸混合物聚合成聚乳酸的工艺技术路线和聚合技术方案;1.工艺技术路线:本“方案二”可采用两种工艺技术路线,完成乳酸聚合成聚乳酸。 Scheme II (two-stage polymerization genus) polymerized into lactic acid or a mixture of polylactic acid technology and route programs polymerization techniques; Technology Route 1: present, "Solution 2" technology employed two kinds of routes, to complete the polymerization of polylactic acid .

乳酸中加入扩链剂和纳米单金属催化剂,经常规加热减压或热传导介质负压对流排气微波辐射旋转加热常压脱水扩链缩聚成低聚物,低聚物加入纳米双金属催化剂经常规加热减压或热传导介质负压对流排气微波辐射旋转加热常压高温裂解蒸馏得粗丙交酯,粗丙交酯从结晶纯化得丙交酯,丙交酯加入纳米单金属催化剂经热传导介质微波辐射旋转加热常压聚合制得聚乳酸。 Lactic acid of chain extenders and nano single metal catalysts, by conventional heating under reduced pressure or negative pressure convection heat transfer media heated exhaust atmospheric microwave radiation dewatering rotation chain polycondensation oligomers, oligomer addition of nano-metal catalyst by conventional heating under reduced pressure or negative pressure convection heat transfer media heated exhaust rotary microwave pyrolysis of atmospheric distillation of crude lactide from the crude lactide is purified by crystallization to give lactide, lactide single nano-metal catalyst was added to the heat transfer medium microwave radiant heating rotatable pressure polymerization of polylactic acid.

2.工艺技术阐述本“方案二”乳酸的类型,乳酸的混合物及纯度与“方案一”相同。 2. The present technology set forth, "Solution 2" type of lactic acid, lactic acid and mixtures thereof, and the purity of "Program a" same.

本“方案二”可选用的纳米级催化剂及普遍催化剂与“方案一”基本相同。 This "Scheme II." Optional catalysts and universal nano-catalyst "Program a" substantially identical.

本“方案二”使用的“多步添加”“纳米级催化剂”和普遍催化剂的方法与“方案一”基本相同。 This "Option II" using "multi-stage '' is added to the methods and catalysts generally" "nanoscopic catalyst program a" substantially identical.

本“方案二”使用的“热传导介质负压对流排气微波辐射旋转加热”的工艺技术方法与“方案一”基本相同。 "Convection heat transfer medium vacuum exhaust rotary microwave heating" of the present, "Solution 2" used technology and methods, "Program a" substantially identical.

3.乳酸两种工艺技术路线聚合成聚乳酸的方法说明方法一:乳酸脱水缩聚:乳酸脱水缩聚可采用常规加热减压或常压除水缩聚工艺,即控制适当的真空度和温度及扩链剂、两性“纳米级催化剂”的条件下,进行减压或常压除去乳酸中的水份,并且对乳酸缩聚物进行预扩链。 3. The two kinds of lactic acid technology route polylactic acid polymerized to a method described method: dehydrating polycondensation of lactic acid: dehydrating polycondensation of lactic acid was heated under reduced pressure or normal using conventional polycondensation process water, i.e., in addition to appropriate control of temperature and degree of vacuum and a chain extender agent, under conditions amphoteric "nano-catalyst", under reduced pressure or atmospheric moisture removing lactic acid, and lactic acid pre-polycondensate chain extender. 常规加热除水缩聚温度为80-120℃,真空度为10-110mmHg,脱水缩聚120min。 In addition to conventional heating water condensation temperature 80-120 ℃, vacuum degree of 10-110mmHg, dehydrating polycondensation 120min. 若在常规加热减压或常压脱水缩聚过程中,使用搅拌器辅助搅动物料,可提高除水缩聚效率。 If reduced or normal pressure dehydration polycondensation in a conventional heating process using an agitator agitating auxiliary materials, condensation water removal efficiency can be improved.

高温裂解:以扩链乳酸缩聚物为源料,在常规加热和两性纳米级复合催化剂的催化下,进行减压或常压扩链乳酸缩聚物脱水蒸馏裂解,脱水蒸馏裂解温度为90-250℃,脱水蒸馏裂解过程采用从低温缓慢升至高温的方法,以防止物料脱水蒸馏裂解过程中,物料损耗过多和防止物料碳化。 Pyrolysis: A chain acid polycondensate source material, in a conventional heating and catalytic amphoteric nanocomposite catalysts, under reduced pressure or atmospheric pressure acid polycondensate chain cleavage dehydration distillation, distillation dehydration pyrolysis temperature of 90-250 deg.] C dehydration distillation method cracking process temperature slowly raised from a low temperature to prevent the material cracking during the distillation dehydration, and to prevent excessive material loss carbonized material. 脱水蒸馏裂解真空度为10-110mmHg,裂解时间为30-100min,裂解产物粗丙交酯,经蒸馏水洗涤几次,再经抽滤、乙酸乙酯结晶提纯、干燥,得纯净丙交酯。 Dehydration degree of vacuum distillation cleavage 10-110mmHg, cleavage time is 30-100min, lysates crude lactide, washed several times with distilled water, and then by suction filtration, purification crystallized from ethyl acetate and dried to give the pure lactide.

聚合:在纳米级催化剂的存在下,以丙交酯为原料热传导介质微波辐射旋转加热,在常压下聚合,聚合微波输出功率为50-500W,聚合时间为10--28min。 Polymerization: nanoscopic catalyst in the presence of lactide as a raw material rotation radiant heat conduction microwave heating medium, polymerization under normal pressure, the polymerization microwave output of 50-500W, the polymerization time is 10--28min.

实施例一将150g纯度为85%的L-乳酸和0.6-1.3g的两性纳米级氧化锌催化剂一起,加入到带有搅拌器和减压蒸馏装置的500ml三颈烧瓶中,充分搅拌均匀后,加热,当体系温度达到100℃时开始抽真空,在真空度为60-100mmHg的条件下,搅拌脱水缩聚120min,脱水缩聚完成后,反应体系从100℃缓慢升温至140℃,加入0.3-0.6g的纳米级氧化锌与三氧化二镧组成的双金属催化剂(按质量比1∶0.06-0.2)的催化和真空度为30-90mmHg的条件下,进行脱水蒸馏,尽量蒸馏出反应体系中的水份,当观察已没有水份被蒸馏出来时,将反应体系温度升高至180℃以上,增大真空度,进行裂解反应30-90min,当反应体系温度达到255℃时,反应结束,即得丙交酯。 Example 150g of a purity of 85% with L- lactic acid and amphoteric nano-zinc oxide catalyst of 0.6-1.3g added to 500ml three-necked flask equipped with a stirrer and a vacuum distillation apparatus, stir evenly, heating, when the temperature of the system reaches 100 deg.] C vacuum is applied, the degree of vacuum under the conditions of 60-100mmHg stirred dehydration polycondensation 120min, after the dehydrating polycondensation is completed, the reaction system was gradually heated from 100 deg.] C to 140 deg.] C, was added 0.3-0.6g bimetallic catalyst nano zinc oxide is lanthanum oxide (mass ratio 1:0.06-0.2) catalyst and under a degree of vacuum of 30-90mmHg, dehydrated by distillation, water was distilled off as far as possible in the reaction system parts, when the water observation has not been distilled off, the reaction system temperature was increased to above 180 ℃, increasing the degree of vacuum, 30-90 min for the cleavage reaction, the reaction system when the temperature reached 255 deg.] C, the reaction was completed, to obtain lactide. 将丙交酯经过漂洗,抽率,乙酸乙酯结晶提纯,干燥后,装入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中,再加入0.06-1g的纳米级辛酸亚锡催化剂后,用薄膜密封好烧杯口放入微波辐射旋转加热炉中,在调节微波输出功率为50-500W的条件下,进行聚合10-28min,即得透明物体聚乳酸(PLA)。 After rinsing the lactide, the rate of extraction, purification crystallized from ethyl acetate, dried, and the bottom layer was charged in a beaker containing a heat transfer medium applied coating of silicon carbide, nano-0.06-1g added stannous octoate catalyst was , sealed with a film into a beaker port rotary furnace and microwave radiation, at microwave output power regulating 50-500W, the polymerization 10-28min, to obtain a transparent object of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.1-0.26g的二异氰酸酯及0.6-1.3g的纳米级氧化锌一起,加入到带有搅拌器和减压蒸馏装置的500ml三颈烧瓶中,充分搅拌均匀后,加热,当体系温度达到100℃时开始抽真空,在真空度为60-100mmHg的条件下,搅拌脱水缩聚120min,脱水缩聚完成后,反应体系从100℃缓慢升温至140℃,加入0.2-0.8g的两性纳米级氧化锌与三氧化二锑组成的双金属催化剂(按质量比1∶0.06-0.3)的催化和真空度为30-90mmHg的条件下,进行脱水蒸馏,尽量蒸馏出反应体系的水份。 150g of the second embodiment of a purity of 85% DL- lactic acid and a diisocyanate and 0.1-0.26g nano zinc oxide together with 0.6-1.3g added to 500ml three-necked flask equipped with a stirrer and vacuum distillation apparatus after stir, heated, when the system reaches a temperature of 100 deg.] C vacuum is applied, the degree of vacuum under the conditions of 60-100mmHg stirred dehydration polycondensation 120min, after the dehydrating polycondensation is completed, the reaction system was gradually heated from 100 deg.] C to 140 deg.] C , amphoteric added antimony trioxide and zinc oxide nano 0.2-0.8g bimetallic catalyst composition (mass ratio 1:0.06-0.3) catalytic conditions and degree of vacuum of 30-90mmHg, dehydrated by distillation, as far as possible water was distilled out of the reaction system. 当观察已没有水份被蒸馏出来时,将反应体系升高至180℃以上,增大真空度,进行裂解反应30-90min,当反应体系温度达到255℃时,反应结束,即得丙交酯。 When viewed moisture has not been distilled off, the reaction system was raised to above 180 ℃, increasing the degree of vacuum, 30-90 min for the cleavage reaction, the reaction system when the temperature reached 255 deg.] C, the reaction was completed, to obtain lactide . 将丙交酯经过漂洗,抽滤,乙酸乙酯结晶提纯,干燥后,装入外层和底部涂抹有热传导介碳化硅涂层的烧杯中,再加入0.06-1g的纳米级辛酸亚锡″催化剂后,用薄膜密封好烧杯口放入微波辐射旋转加热炉中,在调节微波输出功率为50-500W的条件下,进行聚合10-28min,即得透明物体聚乳酸(PLA)。 The lactide after bleaching, filtration, purified by crystallization from ethyl acetate, dried, and the bottom layer was charged in a beaker applied via heat conduction in the silicon carbide coating, then stannous octoate is added nanoscale 0.06-1g "catalyst. after the beaker opening sealed with a film into the rotary furnace and microwave radiation, at microwave output power regulating 50-500W, the polymerization 10-28min, to obtain a transparent object of polylactic acid (PLA).

方法二:乳酸脱水缩聚:乳酸脱水缩聚可采用热传导介质负压对流排气微波辐射旋转加热常压脱水缩聚工艺,即控制适当的微波输出功率和扩链剂及两性纳米级催化剂的条件下,进行常压除去乳酸中的水份,并且对乳酸脱水缩聚物进行预扩链。 Method two: dehydration polycondensation of lactic acid: dehydrating polycondensation of lactic acid may be employed convection heat transfer medium vacuum exhaust rotary microwave heating dehydration polycondensation process under normal pressure, i.e., the microwave power control of appropriate agents and the chain extender amphoteric nano-catalyst, for atmospheric moisture removing lactic acid, and dehydration polycondensation of lactic acid was pre chain. 热传导介质负压对流排气微波辐射旋转加热除水缩聚输出功率为50-500W,脱水缩聚30-120min。 Convection heat transfer medium vacuum exhaust microwave radiation dewatering the polycondensation rotatable heating output power 50-500W, dehydrating polycondensation 30-120min.

高温蒸馏:以扩链乳酸缩聚物为原料,在热传导介质负压对流排气微波辐射旋转加热和两性纳米级复合催化剂的催化下,进行常压扩链乳酸缩聚物脱水蒸馏裂解,脱水蒸流裂解微波输出功率为50-750W,脱水蒸馏裂解过程采用从低功率输出缓慢调节至高功率输出的方法,以防止物料脱水蒸馏裂解过程中,物料损耗过多和防止物料碳化。 Distillation temperature: polycondensate of lactic acid in the chain extender as a raw material, under catalytic radiant heat transfer medium is heated rotary vacuum exhaust convection microwave and amphoteric nano composite catalyst, it was subjected to atmospheric acid polycondensate chain cleavage dehydration distillation, dehydration steam cracking stream microwave output of 50-750W, dehydration distillation method cracking process from a low power output to a high power output is slowly adjusted to prevent the material cracking during the distillation dehydration, and to prevent excessive material loss carbonized material. 脱水蒸馏裂解20-90min,裂解产物粗丙交酯,经蒸馏水洗涤几次,抽滤,乙酸乙酯结晶提纯,干燥,得纯净丙交酯。 Dehydration distillation cleavage 20-90min, the crude lactide lysate, washed several times with distilled water, filtered off with suction, purified by crystallization from ethyl acetate and dried to give the pure lactide.

聚合:在纳米级催化剂的存在下,以丙交酯为原料,热传导介质负压对流排气微波辐射旋转加热,常压聚合,聚合微波输出功率为50-500W,聚合时间为10-28min。 Polymerization: nanoscopic catalyst in the presence of lactide as a raw material, a heat transfer medium vacuum exhaust convection heating microwave radiation rotation, normal pressure polymerization, irradiation power 50-500W, the polymerization time is 10-28min.

实施例一将150g纯度为85%的L-乳酸和0.6-1.3g两性纳米级氧化锌催化剂一起,加入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中,充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波加热炉的输出功率缓慢调节升高至50-450W下,加热,常压脱水缩聚20-100min。 Example After a 150g of 85% pure L- lactic acid and 0.6-1.3g of amphoteric nano-zinc oxide catalyst together, and added to the outer bottom of the beaker with a heat transfer medium applied coating of silicon carbide, stir, add microwave radiation with a rotary furnace and convection vacuum exhaust system, the output power of the microwave oven is adjusted slowly raised to at 50-450W, heating, pressure dehydration polycondensation 20-100min. 脱水缩聚完成后,将微波加热炉的输出功率调节升高至50-480W时,加入0.3-0.6g的纳米级氧化锌与三氧化二镧组成的双金属催化剂(按质量比1∶0.06-0.2)的催化下,进行脱水蒸馏,尽量蒸馏出反应体系中的水份,当从观察镜中观察已没有水份被蒸馏出来时,再将微波加热炉的输出功率缓慢调节升高至50-620W,进行裂解反应20-90min,即得丙交酯。 After dehydration polycondensation is completed, the output power of the microwave oven is adjusted to elevated 50-480W, nano zinc oxide was added with lanthanum oxide 0.3-0.6g bimetallic catalyst composition (mass ratio 1:0.06-0.2 ) for the catalyzed dehydration distillation, the reaction system was distilled off as far as possible in the water, when the water has been distilled off is not viewed from the viewer, then the output power of the microwave oven is adjusted slowly raised to 50-620W , cleavage reaction 20-90min, to obtain lactide. 将丙交酯经过几次漂洗、抽滤、乙酸乙酯结晶提纯、干燥后,装入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中,在加入0.06-1g的纳米级辛酸亚锡催化剂后,用薄膜密封好烧杯口,放入微波辐射旋转加热炉中,在调节微波输出功率为50-500W的条件下,进行聚合10-28min,即得透明物体聚乳酸(PLA)。 Lactide after several rinsing, filtration, purified by crystallization from ethyl acetate, dried, and the bottom layer was charged in a beaker containing a heat transfer medium applied coating of silicon carbide, the nanoscale stannous octoate was added in 0.06-1g after the catalyst, the beaker sealed with a film mouth, into the rotary furnace and microwave radiation, at microwave output power regulating 50-500W, the polymerization 10-28min, to obtain a transparent object of polylactic acid (PLA).

实施例二将150g纯度为85%的DL-乳酸和0.1-0.26g的二异氰酸酯及0.6-1.3g的纳米级氧化锌催化剂一起,加入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中,充分搅拌均匀后,放入带有负压对流排气系统的微波辐射旋转加热炉中,将微波加热炉的输出功率缓慢调节升高至50-450W下,加热,常压脱水缩聚预扩链20-100min。 150g of the second embodiment of a purity of 85% DL- lactic acid and a diisocyanate and 0.1-0.26g nano zinc oxide catalyst 0.6-1.3g together and added to the outer bottom of the beaker with a heat transfer medium applied coating of silicon carbide after stirring, evenly into the microwave radiation with a rotary furnace and convection vacuum exhaust system, the output power of the microwave oven is adjusted slowly raised to at 50-450W, heating, dehydration condensation atmospheric pre chain 20-100min. 脱水缩聚完成后,将微波辐射加热炉的输出功率调节升高至50-480W时,加入0.2-0.8g的两性纳米级氧化锌与三氧化二锑组成的双金属催化剂(按质量比1∶0.06-0.3)的催化下,进行脱水扩链蒸馏,尽量蒸馏出反应体系中的水份,当从观察镜中观察已没有水份被蒸馏出来时,再将微波加热炉的输出功率缓慢调节升高至50-620W,进行裂解反应20-60min,即得丙交酯。 After dehydration polycondensation is completed, the output power of microwave radiant heat oven adjusted to elevated 50-480W, amphoteric nano zinc oxide added with antimony trioxide 0.2-0.8g bimetallic catalyst composition (mass ratio of 0.06 catalytic -0.3), and dehydrated chain distillation, distilled out of the reaction system as much as possible in the water, when the water has been distilled off is not seen from the viewer, the output power of the microwave oven and then slowly raised adjustment to 50-620W, cleavage reaction 20-60min, to obtain lactide.

将丙交酯经过几次漂洗、抽滤、乙酸乙酯结晶提纯、干燥后,装入外层和底部涂抹有热传导介质碳化硅涂层的烧杯中。 Lactide after several rinsing, filtration, purified by crystallization from ethyl acetate, dried, and the bottom layer was charged in a beaker containing a heat transfer medium applicator silicon carbide coating. 再加入0.06-1g的″纳米级辛酸亚锡催化剂后,用薄膜密封好烧杯口,放入微波辐射旋转加热炉中,在调节微波输出功率为50-500W的条件下,进行聚合10-28min,即得透明物体聚乳酸(PLA)。 After addition of 0.06-1g "nanoscale stannous octoate catalyst, beaker was sealed with a film mouth, into the rotary furnace and microwave radiation, at microwave output power regulating 50-500W, the polymerization 10-28min, i.e., obtain a transparent object of polylactic acid (PLA).

Claims (10)

1.一种生物降解高分子材料—聚乳酸的制造方法,其特征在于:以乳酸或乳酸混合物为原料,经扩链剂扩链和“多步添加”纳米级催化剂和热传导介质负压对流排气微波辐射旋转加热直接缩聚或开环聚合制成聚乳酸。 1. A biodegradable polymer material - Method for producing polylactic acid, comprising: a mixture of lactic acid or lactic acid as raw materials, the chain extender and chain extender "multistep Add" nanoscopic catalyst and convection heat transfer medium discharge underpressure microwave heating gas directly rotating polycondensation or ring-opening polymerization of polylactic acid formed.
2.根据权利要求1所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述纳米级催化剂包括:由元素周期表中的I族、II族、III族、IV族、V族和镧系中的金属、金属氧化物及金属盐类中的一种或两种或两种的组合或的纳米单金属催化剂或纳米双金属催化剂,或由羧酸盐类与对甲苯基磺酸组成的纳米组合二元催化剂。 The biological degradation of the polymeric material of claims 1 - Method for producing polylactic acid, which is characterized in that the nanoscale catalyst comprising: a Group I of the Periodic Table, II group, III group, IV group, V metal, metal oxide, or a combination of a group and lanthanide series metal salts and one or two or nano-metal catalyst or a single nano-metal catalyst, or a carboxylic acid salt and p-toluene sulfonyl nanocomposite binary catalyst acid.
3.根据权利要求1或2所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述的直接缩聚:乳酸中加入扩链剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热乳酸预扩链脱水处理,在脱水后乳酸中加入纳米双金属催化剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热扩链预缩聚,预缩聚产物加入纳米单金属催化剂经热传导介质负压对流排气微波辐射旋转加热缩聚或聚合得聚乳酸。 The biological claim 1 or claim 2 Biodegradable Polymer - A method for producing polylactic acid, which is characterized in that the direct polycondensation of: lactic acid of chain extenders, by conventional heating or convection heat transfer media vacuum exhaust microwave heating rotatable chain acid pre-dehydration treatment, the nano-metal catalyst is added after the dehydration of lactic acid, by conventional heating or convection heat transfer media vacuum exhaust rotary microwave heating chain precondensation, precondensation product is added to the metal catalyst nano single convection heat transfer medium through the negative pressure exhaust rotary microwave heating to obtain a polylactic acid polycondensation or polymerization.
4.根据权利要求1或2所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述的直接缩聚:乳酸中加入扩链剂和纳米组合二元催化剂,经常规加热或热传导介质负压对流排气微波辐射旋转加热乳酸连续脱水扩链缩聚,缩聚产物加入纳米组合二元催化剂经热传导介质负压对流排气微波辐射旋转加热缩聚或聚合得聚乳酸。 The biological claim 1 or claim 2 Biodegradable Polymer - A method for producing polylactic acid, which is characterized in that the direct polycondensation of: lactic acid of chain extenders and nano binary catalyst composition by conventional heating or thermal conduction vacuum exhaust convection heating medium microwave radiation dewatering the continuous rotation of chain polycondensation of lactic acid, the polycondensation product of adding nano binary catalyst composition by convection heat transfer medium vacuum exhaust rotary microwave heating to obtain a polylactic acid polycondensation or polymerization.
5.根据权利要求1或2所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述的开环聚合:乳酸中加入扩链剂和纳米单金属催化剂,经常规加热减压或热传导介质负压对流排气微波辐射旋转加热常压脱水扩链缩聚成低聚物,低聚物加入纳米双金属催化剂经常规加热减压或热传导介质负压对流排气微波辐射旋转加热常压高温裂解蒸馏得粗丙交酯,粗丙交酯从结晶纯化得丙交酯,丙交酯加入纳米单金属催化剂经热传导介质微波辐射旋转加热常压聚合制得聚乳酸。 The biological claim 1 or claim 2 Biodegradable Polymer - A method for producing polylactic acid, wherein the ring-opening polymerization of: lactic acid of chain extenders and nano single metal catalysts, by conventional heating under reduced pressure convection heat transfer medium or negative pressure exhaust rotatable heating microwave radiation dewatering chain polycondensation of oligomers, oligomer addition of nano-metal catalyst by conventional heating under reduced pressure or convection heat transfer media negative pressure exhaust rotatable heating microwave radiation pyrolysis distillation of crude lactide from the crude lactide is purified by crystallization to give lactide, lactide single nano-metal catalyst was added to the heat transfer medium is heated under microwave irradiation rotary pressure polymerization of polylactic acid.
6.根据权利要求1或2所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于在加入纳米级催化剂的同时可加入金属离子纯化剂MD1024。 The biological claim 1 or claim 2 Biodegradable Polymer - A method for producing polylactic acid, which is characterized in that while the addition of nanoscopic catalyst metal ion may be added purifying agent MD1024.
7.根据权利要求1所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述扩链剂为:二异氰酸酯或季戊四醇或二酸酐或山梨醇或邻苯四甲酸或二环氧化物类或二唑啉类。 The biological degradation of the polymeric material of claims 1 - Method for producing polylactic acid, wherein said chain extender is: a diisocyanate or di-pentaerythritol or sorbitol, or phthalic anhydride or tetracarboxylic acid or diepoxy or two species of oxazolines.
8.根据权利要求1所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述热传导介质负压对流排气微波加热,是利用微波内部加热特点和抽风机形成负压对流,使滤饼内外产生压力梯度排出乳酸中脱水蒸气水份达到加速乳酸脱水的目的,脱水设备的抽风系统一方面可以对流带走水份,另一方面使脱水系统形成负压防止乳酸在高温下产生的酸性气体的散逸。 The biological degradation of the polymeric material of claims 1 - Method for producing polylactic acid, which is characterized in that said heat conducting medium vacuum exhaust convection microwave heating, using microwave heating characteristics of the internal convection and a negative pressure blower, a pressure gradient inside and outside the cake discharging object water vapor removal lactic acid to achieve accelerated dewatering, dewatering equipment ventilation system one can take the convection of water, on the other hand a negative pressure system to prevent dehydration of lactic acid produced at high temperatures acid gas dissipated.
9.根据权利要求1所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述热传导介质可选用碳化硅Sic或耗散型材料。 9. The biological degradation of the polymeric material of claims 1 - Method for producing polylactic acid, which is characterized in that said heat conducting medium can be selected or silicon carbide Sic dissipative material.
10.根据权利要求9所述的生物降解高分子材料—聚乳酸的制造方法,其特征在于所述热传导介质碳化硅粉粒或粉末,直接铺垫在反应器底部或由3比1的比例与TTZF型粘合剂混合均匀后,涂抹或嵌入所制造的耐烧玻璃反应器或陶瓷反应器的有效加载以下,反应器外部和底部或外部和底部的内外层之间。 10. A biological degradable polymer according to claim 9 Material - A method for producing polylactic acid, wherein the heat transfer medium or a silicon carbide powder particles, directly or bedding in the bottom of the reactor by a ratio of 3 to 1 and TTZF after the adhesive uniformly mixed, applied or embedded resistance produced efficiently burned ceramic loaded glass reactor or the reactor, and between the outside of the reactor bottom or outer layer and the inner and outer bottom.
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Cited By (5)

* Cited by examiner, † Cited by third party
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AT506040B1 (en) * 2007-11-14 2012-03-15 Jungbunzlauer Austria Ag Particulate catalyst and catalyst / stabilizer systems for the production of high-molecular homo- and copolyesters of l-, d- or d, l-milkylic acid
CN101608350B (en) 2008-06-20 2012-07-25 东丽纤维研究所(中国)有限公司 Polylactic fiber with high hydrolytic resistance
US8431678B2 (en) 2007-11-14 2013-04-30 Jungbunzlauer Austria Ag Method for producing cyclic diesters of L-, D- and D,L-lactic acid
CN103072958A (en) * 2013-01-31 2013-05-01 哈尔滨工业大学 Preparation method of manganese-base anti-perovskite nitride
EP2905297A1 (en) * 2014-02-10 2015-08-12 Samsung Electronics Co., Ltd Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AT506040B1 (en) * 2007-11-14 2012-03-15 Jungbunzlauer Austria Ag Particulate catalyst and catalyst / stabilizer systems for the production of high-molecular homo- and copolyesters of l-, d- or d, l-milkylic acid
US8431678B2 (en) 2007-11-14 2013-04-30 Jungbunzlauer Austria Ag Method for producing cyclic diesters of L-, D- and D,L-lactic acid
CN101608350B (en) 2008-06-20 2012-07-25 东丽纤维研究所(中国)有限公司 Polylactic fiber with high hydrolytic resistance
CN103072958A (en) * 2013-01-31 2013-05-01 哈尔滨工业大学 Preparation method of manganese-base anti-perovskite nitride
EP2905297A1 (en) * 2014-02-10 2015-08-12 Samsung Electronics Co., Ltd Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid
US9234075B2 (en) 2014-02-10 2016-01-12 Samsung Electronics Co., Ltd. Polylactic acid preparation method, polylactic acid resin prepared using the method, resin composition comprising the polylactic acid resin, and catalyst system for preparing polylactic acid

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